CN100413806C - Preparation method of ferrite permanent magnetic material - Google Patents
Preparation method of ferrite permanent magnetic material Download PDFInfo
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- CN100413806C CN100413806C CNB2006100433766A CN200610043376A CN100413806C CN 100413806 C CN100413806 C CN 100413806C CN B2006100433766 A CNB2006100433766 A CN B2006100433766A CN 200610043376 A CN200610043376 A CN 200610043376A CN 100413806 C CN100413806 C CN 100413806C
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- ferrite
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- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000696 magnetic material Substances 0.000 title abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 238000000465 moulding Methods 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000002994 raw material Substances 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910001960 metal nitrate Inorganic materials 0.000 claims abstract description 9
- 229920005992 thermoplastic resin Polymers 0.000 claims abstract description 8
- 125000000468 ketone group Chemical group 0.000 claims abstract description 7
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 6
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910001289 Manganese-zinc ferrite Inorganic materials 0.000 claims abstract description 6
- 229910001308 Zinc ferrite Inorganic materials 0.000 claims abstract description 6
- JIYIUPFAJUGHNL-UHFFFAOYSA-N [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] Chemical compound [O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[O--].[Mn++].[Mn++].[Mn++].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Fe+3].[Zn++].[Zn++] JIYIUPFAJUGHNL-UHFFFAOYSA-N 0.000 claims abstract description 6
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 6
- 239000011777 magnesium Substances 0.000 claims abstract description 6
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 6
- 239000011572 manganese Substances 0.000 claims abstract description 6
- 230000001105 regulatory effect Effects 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 18
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 11
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 7
- 229920001652 poly(etherketoneketone) Polymers 0.000 claims description 7
- 229920002530 polyetherether ketone Polymers 0.000 claims description 7
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 6
- 239000006247 magnetic powder Substances 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 229920005989 resin Polymers 0.000 claims description 5
- 239000011347 resin Substances 0.000 claims description 5
- 239000004962 Polyamide-imide Substances 0.000 claims description 4
- 229920002312 polyamide-imide Polymers 0.000 claims description 4
- 230000005415 magnetization Effects 0.000 claims description 3
- 229920001643 poly(ether ketone) Polymers 0.000 claims 1
- 230000001070 adhesive effect Effects 0.000 abstract description 7
- 238000005245 sintering Methods 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 5
- 238000010304 firing Methods 0.000 abstract description 4
- 239000000853 adhesive Substances 0.000 abstract description 3
- 238000009766 low-temperature sintering Methods 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000011230 binding agent Substances 0.000 abstract 1
- 229920008285 Poly(ether ketone) PEK Polymers 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000007858 starting material Substances 0.000 description 3
- DSSYKIVIOFKYAU-XCBNKYQSSA-N (R)-camphor Chemical compound C1C[C@@]2(C)C(=O)C[C@@H]1C2(C)C DSSYKIVIOFKYAU-XCBNKYQSSA-N 0.000 description 2
- 241000723346 Cinnamomum camphora Species 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- 235000021355 Stearic acid Nutrition 0.000 description 2
- 229960000846 camphor Drugs 0.000 description 2
- 229930008380 camphor Natural products 0.000 description 2
- 239000002612 dispersion medium Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 2
- 239000012188 paraffin wax Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000008117 stearic acid Substances 0.000 description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
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- Hard Magnetic Materials (AREA)
Abstract
The invention relates to a preparation method of a ferrite permanent magnet material. The method comprises the following steps: adding a binder into the iron oxide magnetic material; adjusting moisture; forming, magnetizing and pressurizing the mixture with the regulated water; and a firing step under high temperature conditions, characterized in that: the magnetic material of the ferrite is selected from a mixture of iron oxide and one or more of manganese-zinc ferrite, manganese ferrite, magnesium ferrite and copper-zinc ferrite, and metal nitrate accounting for 1-2% of the weight of the magnetic material is added into the magnetic material; the adhesive comprises thermoplastic resins with ketone groups, and the weight ratio of the thermoplastic resins to the mixture is 0.1-0.2%; the water content in the mixture of the water content adjusting process is 0.2-0.4%; the temperature of sintering and molding under the high-temperature condition is between 350 ℃ and 450 ℃. The invention has the outstanding characteristics of realizing low-temperature sintering, reducing cost, improving orientation and optimizing magnetic property by improving the raw materials and the adhesive.
Description
Technical field
The present invention relates to the preparation method of ferrite permanent-magnet materials, the preparation method of the oxide magnetic material based permanent magnet of particularly dry formed method moulding.
Background technology
At present, preparation method's method of permanent magnet roughly is divided into the dry formed method and the wet type method of forming.In the wet type method of forming, (as China Patent No. 03116206.1) can make magneticsubstance obtain good orientation, thereby can obtain good magnetic because the permanent magnet pellet rotates in dispersion medium easily.But, can reduce productivity owing in extrusion forming, dispersion medium must be discharged to (outside the mould cavity) outside the molding space; This external demand large mould structure has strengthened cost of equipment.Dry formed method be the permanent magnet material powder filling of drying regime in molding space (die cavity), the method for moulding in magnetic field, this compares with the wet type method of forming, though the poor orientation of magneticsubstance has the productivity height, the advantage that cost of equipment is low.
In the dry formed method, the permanent magnet material in being filled to mould contains tackiness agent usually.This tackiness agent had both required that permanent magnet material was had good adhesive effect, did not hinder magneticsubstance in easy magnetized axial array in magnetic upper edge etc. again.During dry formed method moulding, the tackiness agent of commonplace use is solid paraffin, stearic acid, camphor etc.Though solid paraffin and stearic acid have superior adhesive effect,, exist to hinder the tendency of magneticsubstance in the easy magnetized axial array in magnetic upper edge because adhesive effect is too strong.Though camphor can be effectively as at additional tackiness agent when pressing under magnetic field is arranged because it can distil, make it and the ratio of mixture of ferrite powder can time to time change, thereby can produce the obstruction operations for forming or make the shortcomings such as intensity reduction of in type formed body.
In order to address the above problem, Chinese patent (02803279.9) discloses a kind of manufacture method of oxide magnetic material based permanent magnet, wherein as the dry type pressing under magnetic field with the tackiness agent of ferrite magnet powder, adopt the cured of fatty acid series, and under 1200-1260 ℃ of condition sinter molding.But the subject matter that this method exists is that technology is numerous and diverse, and causes the formation of ferrous ion behind the high temperature sintering easily, specific resistance reduction etc.Not under the extra high situation of requirement particularly, increased cost for the environment for use temperature.
Summary of the invention
The objective of the invention is to utilizing at present the comparatively technical process and the equipment of dry formed manufacturing permanent magnet material commonly used, by improvement to starting material and tackiness agent, a kind of realization low-temperature sintering is provided, reduce cost, can improve the preparation method of the ferriferous oxide magneticsubstance of orientation and optimization magnetic property simultaneously.Technical scheme of the present invention comprises: add tackiness agent and blended tackiness agent interpolation operation in the raw material powder of ferriferous oxide magneticsubstance; Adjusting comprises the moulding of above-mentioned raw materials powder and tackiness agent and regulates operation with the moisture of moisture in the mixture; The above-mentioned moulding that moisture is regulated adds in the mould with mixture, applies magnetic field, makes the oxide magnetic powder along dry formed operation in the magnetic field of direction of magnetization arrangement pressurization simultaneously easily; And the ablating work procedure of under hot conditions, in type formed body being fired, it is characterized in that: the magneticsubstance of described iron compound is selected from one or more the mixture in ferric oxide and manganese-zinc ferrite, manganese ferrite, magnesium ferrite, the copper-zinc ferrite, and adds at above-mentioned magneticsubstance and to account for the metal nitrate that the magneticsubstance weight ratio is 1-2%; Described tackiness agent comprises the type thermoplastic resin with ketone group, and its weight ratio in mixture is 0.1-0.2%; Moisture content in the mixture of above-mentioned moisture adjusting operation is 0.2-0.4%; The temperature of sinter molding is between 350-450 ℃ under the described hot conditions.
Above-mentioned type thermoplastic resin with ketone group comprises polyether-ether-ketone (PEEK), polyetherketone (PEK), PEKK (PEKK), polyamide-imide resin.
Above-mentioned metal nitrate comprises one or more mixture of iron nitrate, nickelous nitrate, zinc nitrate, cupric nitrate, Xiao Suangu.
Outstanding feature of the present invention is by the improvement to starting material and tackiness agent, realizes low-temperature sintering, reduces cost, and can improve orientation simultaneously and optimize magnetic property.
Embodiment
It is basic identical that preparation method's master operation of ferrite permanent-magnet materials of the present invention and present dry formed legal system are equipped with magneticsubstance, also comprises: add tackiness agent and blended tackiness agent interpolation operation in the raw material powder of ferriferous oxide magneticsubstance; Adjusting comprises the moulding of above-mentioned raw materials powder and tackiness agent and regulates operation with the moisture of moisture in the mixture; The above-mentioned moulding that moisture is regulated adds in the mould with mixture, applies magnetic field, makes the oxide magnetic powder along dry formed operation in the magnetic field of direction of magnetization arrangement pressurization simultaneously easily; And the ablating work procedure of under hot conditions, in type formed body being fired.
Wherein the magneticsubstance of oxide compound is selected from one or more the mixture in ferric oxide and manganese-zinc ferrite, manganese ferrite, magnesium ferrite, the copper-zinc ferrite, and adds in above-mentioned magneticsubstance and account for the metal nitrate that the magneticsubstance weight ratio is 1-2%; Described tackiness agent comprises the type thermoplastic resin with ketone group, and its weight ratio in mixture is 0.1-0.2%; Moisture content in the mixture of above-mentioned moisture adjusting operation is 02-0.4%; The temperature of sinter molding is between 350-450 ℃ under the described hot conditions.
Above-mentioned type thermoplastic resin with ketone group comprises polyether-ether-ketone (PEEK), polyetherketone (PEK), PEKK (PEKK), polyamide-imide resin.
Above-mentioned metal nitrate comprises one or more mixture of iron nitrate, nickelous nitrate, zinc nitrate, cupric nitrate, Xiao Suangu.
Above-mentioned metal nitrate comprises one or more mixture of iron nitrate, nickelous nitrate, zinc nitrate, cupric nitrate, Xiao Suangu.
Several representative instances (percentage ratio is total amount per-cent in the table, temperature unit ℃) have been enumerated in the table
| Example | Ferric oxide | Manganese-zinc ferrite | The manganese ferrite | The magnesium ferrite | Copper-zinc ferrite | Iron nitrate | Nickelous nitrate | Zinc nitrate | Cupric nitrate | Xiao Suangu | Resin content | Sintering temperature |
| 1 | 61％ | 37％ | 1.8％ | 0.2％ | 360 | |||||||
| 2 | 65％ | 15％ | 18.2％ | 1.2％ | 0.5％ | 0.1％ | 385 | |||||
| 3 | 29.3％ | 48％ | 21.1％ | 0.5％ | 1.0％ | 0.1％ | 425 | |||||
| 4 | 60％ | 20％ | 10％ | 3.0％ | 5.4％ | 0.4％ | 1.2 | 0.2％ | 450 | |||
| 5 | 75％ | 14％ | 9.2％ | 1.5％ | 0.2％ | 0.1％ | 350 |
Starting material are prepared
Main raw material(s) can directly adopt gets the finished product of purity more than 99%, below the granularity 450 μ m.The blending ratio of one or more in the main raw material in ferric oxide and manganese-zinc ferrite, manganese ferrite, magnesium ferrite, the copper-zinc ferrite does not have strict restriction, choose here several mainly taking cost into account.Iron nitrate, nickelous nitrate, zinc nitrate, cupric nitrate or Xiao Suangu are selected purity 99.9% for use, can directly mix with dry powder with main raw material, mix with main raw material after also can being dissolved in water, here the main effect of nitrate comprises two aspects, the one, promote follow-up sintering and prevent that material from forming excessive crystal grain, the 2nd, cooperate the improvement formability with tackiness agent, improve magnetic property, studies have shown that its addition shows as optimum regime at 1-2%.Polyether-ether-ketone (PEEK), polyetherketone (PEK), PEKK (PEKK), polyamide-imide resin have good adhesive and long-term heatproof characteristic, as the tackiness agent use of can choosing arbitrarily or arrange in pairs or groups, no matter but the sort of tackiness agent among the present invention, must strictly control its addition in use, very fewly be difficult to play adhesive effect, reduce the heatproof characteristic too much again, be preferably in 0.1-0.2%.
When the raw material powder of magnetic powder mixes with tackiness agent, can take the blending means of liquid or solid state.When adopting liquid tackiness agent, at first become solution to mix by proportioning in nitrate, so in this process, just can control water-content in the mixture by controlling warm-up time and ambient moisture with tackiness agent.
Moisture content in the mixture of moisture adjusting operation will be controlled at 0.2-0.4%.The moisture metering needle is to above-mentioned two kinds of situations, to the moulding that comprises above-mentioned raw materials powder and tackiness agent with carrying out the moisture that adding deduct of moisture regulated this mixture in the mixture.Mixed moulding has a significant impact formability and magnetic with the moisture of mixture.Water deficient, original form just is hard to keep when sinter molding; Moisture content is too high, and magnetic powder can condense, and hinders magnetic powder particles to be easy to reduce magnetic along magnetized axial array on magnetic.
The mixture that regulates moisture adds die for molding, applies the magnetic field of 7000oe simultaneously, and pressure is 1 ton/square centimeter to be suppressed.The forming composition of Xing Chenging is fired again like this.The scope that firing temperature is 350 1 450 ℃ gets final product, and be about 2-4 hour the steady time of firing, need not thousands of degree high temperature sinterings.Certainly will cause the volatilization of some elements and cause specific resistance to reduce when firing temperature is too high.Distinctive feature of the present invention has adopted the characteristic of the tackiness agent and the metal nitrate of high coherence degree just, less than 500 ℃ the time, just can obtain the magnet of high-density, excellent magnetic.
The permanent magnet sample that adopts aforesaid way to make, the density 4.5-4.9 of fired body, magnetic flux 3000-3200.The agglomerating requirement that also reaches a high temperature substantially of other every indexs.Experimental results show that the present invention can obtain the especially excellent effect that prior art had not had, its product can meet the service requirements of every field to permanent magnet.
Claims (3)
1, a kind of preparation method of ferrite permanent-magnet materials, step comprises: add tackiness agent and blended tackiness agent interpolation operation in the raw material powder of ferriferous oxide magneticsubstance; Adjusting comprises the moulding of above-mentioned raw materials powder and tackiness agent and regulates operation with the moisture of moisture in the mixture; The above-mentioned moulding that moisture is regulated adds in the mould with mixture, applies magnetic field, makes the oxide magnetic powder along dry formed operation in the magnetic field of direction of magnetization arrangement pressurization simultaneously easily; And the ablating work procedure of under hot conditions, in type formed body being fired, it is characterized in that: the magneticsubstance of described ferriferous oxide is one or more the mixture in ferric oxide and manganese-zinc ferrite, manganese ferrite, magnesium ferrite, the copper-zinc ferrite, and adds in above-mentioned magneticsubstance and account for the metal nitrate that the magneticsubstance weight ratio is 1-2%; Described tackiness agent comprises the type thermoplastic resin with ketone group, and its weight ratio in mixture is 0.1-0.2%; Moisture content in the mixture of above-mentioned moisture adjusting operation is 0.2-0.4%; The temperature of sinter molding is between 350-450 ℃ under the described hot conditions.
2. the preparation method of ferrite permanent-magnet materials according to claim 1, it is characterized in that: above-mentioned type thermoplastic resin with ketone group comprises polyether-ether-ketone, polyetherketone, PEKK, polyamide-imide resin.
3. the preparation method of ferrite permanent-magnet materials according to claim 1 is characterized in that: above-mentioned metal nitrate comprises one or more mixture of iron nitrate, nickelous nitrate, zinc nitrate, cupric nitrate, Xiao Suangu.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100433766A CN100413806C (en) | 2006-03-31 | 2006-03-31 | Preparation method of ferrite permanent magnetic material |
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100433766A CN100413806C (en) | 2006-03-31 | 2006-03-31 | Preparation method of ferrite permanent magnetic material |
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| CN1834060A CN1834060A (en) | 2006-09-20 |
| CN100413806C true CN100413806C (en) | 2008-08-27 |
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| CNB2006100433766A Expired - Fee Related CN100413806C (en) | 2006-03-31 | 2006-03-31 | Preparation method of ferrite permanent magnetic material |
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| EP3249664B1 (en) * | 2015-01-22 | 2019-12-04 | Alps Alpine Co., Ltd. | Powder core, method for producing same, electric/electronic component provided with same, and electric/electronic device having said electric/electronic component mounted thereon |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139648A (en) * | 1995-07-06 | 1997-01-08 | 南京理工大学 | Preparation method for ultra thin hexagonal crystal system ferrite |
| CN1323046A (en) * | 2001-06-07 | 2001-11-21 | 东南大学 | Composite nanometer magnetic titania material with Mn-Zn ferrite and its prepn |
| CN1347855A (en) * | 2001-11-27 | 2002-05-08 | 南京大学 | Zinc ferrite material with giant magnetic resistance effect and its prepn |
-
2006
- 2006-03-31 CN CNB2006100433766A patent/CN100413806C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1139648A (en) * | 1995-07-06 | 1997-01-08 | 南京理工大学 | Preparation method for ultra thin hexagonal crystal system ferrite |
| CN1323046A (en) * | 2001-06-07 | 2001-11-21 | 东南大学 | Composite nanometer magnetic titania material with Mn-Zn ferrite and its prepn |
| CN1347855A (en) * | 2001-11-27 | 2002-05-08 | 南京大学 | Zinc ferrite material with giant magnetic resistance effect and its prepn |
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| CN1834060A (en) | 2006-09-20 |
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